Copper containing azodyestuff



Patented Dec. 19, 1933 COPPER CONTAINING AZODYESTUFF Richard Stiisser, Cologne-Deutz, Germany, as-

signor to General Aniline Works, Inc., New

York, N. Y.,'a corporation of Delaware No Drawing. Application September 29, 1931, Serial No. 565,918, and in Germany October 15,

12 Claims. (Cl. 260-'12) The present invention relates to a process of preparing azodyestuffs containing copper in a complex form and to the products obtainable thereby.

According to my invention azodyestufis containing copper in a complex form are prepared by treating an azodyestuff containing an alkoxy group in ortho-position to at least one diazotized amino group, said diazotized amino group being coupled with a coupling component suitable for producing azodyestufis in ortho-position to a hydroxyl group, alkylaminoor phenylamino, group as substituent of said coupling component, with an agent yielding copper in a solvent for said azodyestuif in the presence of an organic base, under such conditions that the alkoxy group is split up with the formation 0 a copper containing azodyestufl. As starting azodyestuifs there may be enumerated by way of example the following types:

RN=NR wherein R means a diazotization component, containing in ortho-position to the diazotized (middle component) and R" stands for the radical of a coupling component, and wherein R or R, or R and R. contain an alkoxy group or alkoxy groups respectively in orthoposition to their diazotized amino group or 5 -groups the components to which the said diazotized amino groups are attached bearing in ortho-position to the azo-bridge a hydroxy, alkylaminoor phenylamino group as substituent; R-N=NR'N=NR, wherein R stands for a radical of a diazotization component, R stands for a coupling component coupling twice and R. stands for a diazotization' component, the components being selected in such a manner that at least once there is present in the molecule the grouping:

N=N- -diazotization component coupling component N Oa1k T alk meaning an alkyl group and a: standing for a hydroxy-, alkylaminoor phenylamino' group. 7

In carrying out the invention the dyestuff to be coppered is dissolved in a suitable solvent, such as for example, in water, ethyl alcohol, a

mixture of water and ethyl alcohol, benzene, and

to the azodyestufi dissolved there is added an organic base, such as pyridine, hexahydroethylaniline, dimethylamine, etc,; the quantity of the organic base added may be varied within the widest limits, generally I add about 10 to about 50% of'the organic base. In case the dyestufi is soluble in the pure base, the coppering may be performed in the base without the addition of Then the necessary quantity of the copper compound yielding copper, such as a suitable salt of monoand divalent copper, is added, and the whole is heated at temperatures .between about 50 and 170 C. until the alkoxy group or -groups present in the molecule have been split up with the formation of the copper compound of the azodyestuflf. The temperature required for my new coppering process depends somewhat upon the constitution of the starting dyestuff, and every one skilled in the art will find another base.

out the suitable temperature.

The proceeding of the coppering process is connected with a change in the coloration of the azodyestufi, and the process is finished when. the coloration no longer alters. ess is complete in 1 to 2 hours. method of carrying out the process consists in refluxing the reaction mixture for the period required, but it is to be understood that in cases where temperatures higher than the boiling point are required, the process'is to be carried out under pressure.

My copper compounds are generally powders of various shades, and if they contain a sulfonic acidor carboxylic acid group soluble in water, dyeing fibres various shades of good fastness properties.

pyridine.

lowing formula:

Generally the proc A preferred tionno longer takes place.

pound of the dyestuff' having in its free state is filtered and dried. In this manner a dark powder is obtained which dyes wool Bordeaux red.

Example 2.20 gramsof thedisazodyestuff from 2 molecular proportions of Z-amino-l-methoxybenzenel-sulfonic acid and one molecular proportion of 5.5 -dihydroxy-2.2 -dinaphthylamine 7.'7-disulfonic acid are boiled for 2 hours under reflux in one litre of water with 8 grams of cuprous chloride and 40 cos. of pyridine. The original bluish red solution becomes continuously more violet until after 2 hoursboiling the coloration of the dyestuif no longer alters. By salting out and filtering, a copper compound having in its free state the following formula:

HOaS

is obtained-Which after drying dissolves in water with a violet coloration and dyes cotton, silk and viscose silk violet shades. The dyeings are fast to alkali and very fast to light.

is rlltered off, dissolved in hot water by means of caustic soda lye, filtered and salted out from the filtrate. After filtering and drying, a dark powder is obtained, which dissolves in water with a violet coloration and dyes cotton a violet shade, fast to light. 7

Example 6.--20 grams of the disazodyestufi from 2 molecular proportions of 2-aminolmethoxybenzenel-sulfonic acid and one molecular proportion of 5.5dihydroXy-2.2-dinaphthylurea-Yf?'-disulfonic acid are boiled under reflux in one litre of water with 16 grams of copper sulfate and 49 cos. of pyridine until the coloration no longer alters. The copper compound of the dyestuff separates out, it is filtered and dried.

It is a powder, which dyes cotton, silk and viscose silk in bluish red shades, fast to alkalies and light. In its free state the copper compound of the dyestulr" has the following formula:

Example 3.By replacing the pyridine in Example 2. by. dimethylamine a dyestuff is likewise obtained, which dyes cotton, silk and viscose silk violet. shades.

Example 4.By replacing the pyridine in Example. 2.by hexahydroethylaniline a reddish violet dvestufil is obtained after prolonged boiling, whichv dyes cotton, silk and viscose silk violet shades. f

Example '5.30, grams of the azodyestufi from onemolecular. proportion of Z-amino-l-methoxybenzene 4-sulfo-methylamide, 'one molecular sessing in its free state the following formula:

' N=COH3 H3CC=N Q l 3 N V N SOaH 0 -0-1 N- N If- =C I 2/ \J I H035 0 Cu 0 ()Cu -0 proportion of 7 5.5-dihydroxy-2.2'-dinaphthylamine-7.7-disulfonic acid and one molecular v proportion of 2-amino-1-methoxybenzene-4-sul- Ionic acid-are boiled under reflux in one litre water with 15 grams of copper sulfate and 50" cos. of pyridineuntil a change in the colora- The copper comthe following formula:

and dyeing cotton,'silk and viscose silk in bluish red shades, fast to alkalies and light. 7

Example 8.-20 grams of the disazodyestuff from 3.3 dim-ethoxy L4-diaminodiphenylurea After working up, a dark powcopper compound or the dyestuif possesses .the following formulay of 5.5 dihydroxy-2.2'-dinaphthylamine-7.7'-disulfonic acid are dissolved in llitre of hot water soul coat I l/ 1 O-C11-O I V O-C11-O Example 9.--20 grams of the az'odyestuff preand refluxed for about 2 hours with the addition pared from one molecular proportion of diazoof 50 cos. of pyridine and 15 grams of copper tized S-nitro-Z-amino-l-hydroxybenzene-methylsulfate. During the process the coloration of the ether-4-sulfonic acid and one molecular proporsolution is turned to greenish-blue. The copper tion of 2 phenylaminonaphthalene 6 sulfonic compound of the dyestufi having in the free state acid are heated with one litre of water, 20 ccs. of the following formula:

' on on H03s\ NH It 7 OH; soan 0-611 0 2 pyridine and 10 grams of copper sulfate for about is filtered; i e-dissolved in hot water, filtered after 1 hour under reflux. The copper compound havcooling and dried. In form of its alkali metal ing in its free state the following formula: salts it is a black powder, soluble in water with a so H blue coloration, dyeing the vegetable fibre blue 2 shades of good fastness to ironing and light. SOIH I Iclairn: r 1105 g l. The process which comprises heating an am- 0 N dyestufi containingat least once the grouping l 1/ 1 N=N 0--C\1- "N diazotization component} (lleoupling component 0alk a:

is filtered and dried. It is a dark powder, soluble in water with a violet coloration.

Example 10.20 grams of the azodyestuff prepared from one molecular proportion of diazotized aniline-Z-sulfonic acid and. one molecular proportion of l-amino-Z ethoxynaphthalene-S- sulfonic acid, further diazotized and coupled with one molecular proportion of 2-phenylamino-5-hydroxynaphthalene-T-sulfonic acid are refluxed for about 3 hours in one litre of water with the addition of 200 cos. of pyridine and 20 grams'of copper sulfate. The copper compound of the dyestuff which has partially separated is completely precipitated by the addition of common salt, filtered, re-dissolved in hot water, salted out and dried. The dyestuff having in its'free state the following formula:

wherein "alk stands for an alkyl group and :1: stands for a hydroxyalkylamino or phenylarnino group, in solution in the presence of an organicbase and with the addition of an agent yielding copper until the alkoxy group has been split up with the formation of a copper compound of the azodyestufi.

2. The process which comprises heating an azodyestulf containing at least once the grouping \CN=NO/ diazotization componentg3 1 coupling component 0-alk x wherein elk stands for an alkyl group and :1: stands fora hydroxy-', alkylaminoor phenylamino group, in solution in the presence of an organic base and with the addition of a watersoluble salt of monoor bivalent copper-at a temperature between 50 and 170 C.=until the alkoxy soul HOaS NH@ z s'o H 1" is in form of its alkali metal salt a dark powder, soluble in water with a bluish coloration dyeing the vegetable fibre blue shades of good fa'stness properties.

Example 11.-20'grams of the azodyestuff' prepared from two molecular proportions of diazotized 1.3-dimethyl 4 aminobenzene-S-sulfonic acid, coupled with two molecular proportions of 1-methyl-4-methoxy-3-aminobenzene, again diazotized and coupled with 1 molecular proportion diazotization component I stands for' a hydroxya alkylaminoor phenylamino-.group, insolution in the presence of an organic base of the group consisting of pyridine, hexahydroethylaniline, dimethylamine at a temperature between 50 and 170 C; until the alkoxy group has been split up with the formation of a copper compound of the azodyestufi.

4. The process which comprises dissolving an azodyestuff containing at least once the grouping q C-N=N,C diazotization component coupling component Oalk 22 wherein alk stands for an alkyl group and :r

stands for a hydroxy-, alkylaminoor phenylamino group, in aqueous pyridine and heating the same with the addition of a watersoluble salt of monoorbivalent copper at a temperature between 50 and'l'lO C. for about 1 to 2 hours.

' 5. The process which comprises dissolving a dyestuiT of the general formula:

phenyl'amino group, in aqueous pyridine and heating with the addition of copper sulfate at a temperature between 50 and 170 C. until the alkoxy group has been, split up.

6; The process which comprisesrefluxing the azodyestufi of the formula:

tion components, the Rs stand for radicals ofdiazotized coupling components, 'R," stands for the radical of a coupling component coupling twice, the alks stand for alkyl groups, the alkoxy groups standing in ortho-position to the azo groups attached to R", the xs standing in orthoposition to the azobridges and meaning the hydroxy, alkylaminoor phenylamino groups, in aqueous pyridine and heatingwith the addition of copper sulfate at a temperature between 50 and 170 C. until the alkoxy groups have been split up.

8. The process which comprises refluxing the azodyestuif of the formula:

in aqueous pyridine with the addition of copper sulfate for about 2 hours.

9. Copper containing azodyestufi's being char: acterized by containing at least once the grouping wherein R stands for a radical of a diazotization component, B stands for a diazotized coupling component, R" stands for a radical of an end component, :r stands for oxygen, N-alkyl or N-phenyl, the grouping standing in ortho-position to the azo-bridge N=N, being generally dark powders, yielding dyeings of good fastness properties.

10. The copper containing azodyestuff of the following formula:

SOaH

Hols

being in form of its alkali metal salt a dark powder, soluble in water with a bluish coloration and dyeingthe vegetable fibre blue shades of 1 good fastness properties.

soln

H03s NH- QN=N- -N=N 03H 'C2H5 )H inv aqueous pyridine with the addition of copper 11. Copper containing azodyestuffs of the gensulfate for about 3 hours. eral formula: v

7. The process which comprises dissolving an azodyestufi of the general formula: j

R-N=NRNN-RN=N '-N=N-R' 'O Ouz I wherein the Ris stand for radicals of diazotization O 1k x 9 components, the R'.s stand for radicals of diazowherein theiRs stand for radicals of diazotiza.-. tized coupling components, R" stands for a radical of a. coupling component coupling twice, the :z's stand for oxygen, N-allgvl or N-phenyl, the groupings being in form of its alkali metal salts a black powder, soluble in water with a. blue coloration and dyeing the vegetable fibreblue shades of good fastness to ironing and light.

RICHARD sTtissER. 

